Chapter 6 Summary and Conclusions Plasma deposited amorphous hydrogenated carbon films (a-c:h) still attract a lot of interest due to their extraordinary properties. Depending on the deposition conditions (applied power, gas pressure, gas flow rate and bias voltage, temperature, and the gas composition) the films can vary from hydrogenated soft polymer-like via hard diamond-like carbon to pure carbon based tetrahedral amorphous and diamond modifications. The properties of a-c:h films are mainly determined by the bonding hybridization ratio of the carbon atoms in the different hybridization states, i.e. sp 3 : sp 2 : sp 1, and by the hydrogen content. Carbonaceous plasma grown nanoparticles attract a similarly high attention as a-c:h films do. During the fabrication of integrated circuits from reactive plasmas nanoparticles may be spontaneously created inside the plasma reactor, causing often damage of the devices. On the other hand, in fabrication of nanocrystalline materials, incorporation of nanoparticles into the film matrix improves the films properties. During the plasma processing hydrogen molecules and atoms are created inherently in all hydrocarbon discharges through the dissociation of precursor molecules. Hydrogen atoms acting together with ions during the film growth can activate or deactivate the surface processes through the creation of dangling bonds or their saturation, leading to an enhancement (synergistic effect) or a reduction (anti-synergistic effect) of the growth speed. Hydrogen atoms also influence the particle formation. These effects are observed and studied in this work. In order to achieve a better understanding of the role hydrogen atoms play in the formation of carbon based nanoparticles and on the growth/etching speed of the amorphous hydrogenated carbon films experiments were performed with a specially designed double plasma setup. It consists of two combined plasmas. One plasma is used as a source of active species created in the dissociation processes of the precursor gas molecules for the particle formation or for the film deposition. In the case of nanoparticle formation it is an inductively coupled plasma and in the
case of the investigation of film deposition/etching speed it is a microwave expanding plasma. As a precursor gases are used methane and acetylene. The spatial afterglow of a fully recombined surface wave plasma (second plasma) is used as an independent and controllable source of additional flux of hydrogen atoms. Here the working gas is a flow of molecular hydrogen. To observe the time evolution of the dust particle formation, in-situ monitoring of the intensity of scattered laser light coming from the discharge is measured while the size and topography of dust particles are investigated ex-situ by means of the secondary electron microscope. The chemical composition of the plasma during the process is monitored by rest gas analyzer (neutrals) and plasma process monitor (positive ions) mass spectrometers. The measurements of the intensity of scattered laser light show that particles in acetylene discharge spontaneously start forming soon after the discharge is ignited and that particles periodically grow and disappear from the discharge. The particles grown in this inductively coupled discharge have a very broad size distribution and a very smooth surface. The particle growth speed is very high and a few particle generations exist at the same time in the discharge. All this strongly contrasts the situation in capacitively coupled discharge where particles have the growth speed of nm/min order, particles are almost monodisperse and have cauliflower shape. During this phase of the experiment the second discharge is switch off, thus only the hydrogen molecules are injected into the acetylene plasma. The situation drastically changes after the ignition of plasma in molecular hydrogen and the injection of additional flux of hydrogen atoms in the acetylene plasma. Any further particle formation is completely suppressed as long as the hydrogen discharge is on, i.e. the additional amount of hydrogen atoms is injected in the acetylene discharge. After the switching off of molecular hydrogen discharge, i.e. again injecting only hydrogen molecules to the acetylene discharge, the formation of particles starts again spontaneously. A key to the understanding of this effect is the plasma chemistry. From previous work we know that C 2 H radicals are the precursors for driving the polymerization reactions. These radicals, created in an electron induced dissociation reaction: are destroyed in reaction with hydrogen atoms: C 2 H 2 + e C 2 + H + e, (6.1) C 2 H + H C 2 H 2, (6.2) which likely appears to be the most important due to the relatively large cross 85
section of this reaction and very high concentration of C 2 H radicals. Acting on this way, hydrogen atoms suppress the particle formation in the very early phase of their genesis the chemical phase. This is confirmed by measuring the mass spectra of neutrals and positive ions. The behavior of the neutral mass spectra in the acetylene discharge with the addition of hydrogen molecules correlates with the periodicity of particle formation. The injection of additional flux of hydrogen atoms influences the chemical composition of the plasma. More precisely, two groups of masses can be differentiate. In one group are masses whose intensity decreases after the additional injection of hydrogen atoms, as it is the case for the masses m = 50 (biacetylene) and m = 74 (triacetylene). In the second group are the masses whose intensity decreases, as mass m = 78 (benzene, C 6 H 6 ), for example. The positive ion mass spectra expresses a similar behavior. Most of the masses experience a decrease after the injection of additional amount of hydrogen atoms. However, in the case of positive ions the explanation is not straightforward due to at least two reasons. One reason is that the plasma process monitor measures the flux and not the concentration of positive ions. The second one is that the presence of particles itself influences the plasma parameters and the sheath properties, while the additional flux of hydrogen atoms influences both of them, thus it is not possible to make a distinction between these two influences when they act at the same time. To eliminate the influence of particles on the plasma parameters and the sheath properties, the same experiment is performed under the same experimental conditions but with a reduced flow of acetylene when the particle formation is not observed. The same tendency in formation of higher mass hydrocarbon positive ions exists hydrogen atoms suppress the polymerization process of higher hydrocarbon positive ions. The second part of this work is dedicated to investigations of the influence of hydrogen atoms, impinging onto the surface, on the deposition and etching speeds of hydrogenated carbon films and on the influence of hydrogen atoms on the film properties and the structure under plasma conditions. For this investigations a rearranged double plasma setup is employed. The atomic hydrogen source is the same as in the previous experiment but for the creation of active species for deposition/etching process this time an expanding microwave plasma is employed. As precursor gases methane and acetylene are used. Presented data show that hydrogen atoms strongly influence processes on the surface on the way that the deposition speed decreases and the etching speed increases for one order of magnitude in the presence of an additional flux of hydrogen atoms. 86
This is in agreement to the literature, where similar anti-synergistic and synergistic effects, respectively, are observed in experiments with well defined beams of ions, radicals and hydrogen atoms. Here, we demonstrated that under the plasma conditions. The decrease of the deposition speed arises due to passivation of the created dangling bounds at the surface by impinging hydrogen atoms. While the hydrogenation during the film deposition in methane, maximally saturated (hydrogenated) hydrocarbon, occurs due to hydrogenation of the broken C C bonds by impinging argon ions, that also has as a consequence a shortening of the carbon chains, hydrogenation by incoming hydrogen atoms during the film deposition in acetylene, maximally unsaturated hydrocarbon, mainly occurs via hydrogenation of unsaturated sp 2 carbon groups increasing the amount of sp 3 hybridized carbon atoms mainly bonded in the polymeric (CH 2 ) groups. Hydrogenation results also in the softening of the film. In the case of the enhancement of the etching speed, during the simultaneous action of Ar + ions and additional H atom flux, the synergism is explained by the process of chemical sputtering. Incoming H atoms passivate dangling bonds not only on the surface but also within the ion penetration range of the energetic Ar + ions, creating C x H y species. This species then diffuse to the surface and desorb. Since this process occurs not only at the surface but also within the whole ion penetration range it is more efficient then when the passivation of dangling bonds occurs only at the surface. Incoming hydrogen atoms are incorporated also in the bulk of the film during the growth process and influence its structure. One consequence in the increase of the hydrogen content, reducing the film density and the change in the film structure. The Raman spectra of films deposited in the mixture of methane with addition of molecular and atomic hydrogen show that incorporated hydrogen atoms reduce the size of the sp 2 phase which can exist in ring or chain form and slightly influence the trans-polyacetylene phase in the film. On the other hand Raman spectra of the films deposited in acetylene discharges with addition of molecular and atomic hydrogen revealed almost complete destruction of the sp 2 graphitic sites via the saturation of C=C bonds by incoming hydrogen atoms toward the increase of the sp 3 phase ( CH x groups) and the amount of bonded hydrogen atoms. This is supported by the infrared spectra revealing additional incorporation of hydrogen atoms in presence of the hydrogen atoms flux. This conclusion is also in good agreement with the decrease of the refractive index n and the extinction coefficient k indicating higher hydrogenation of the film caused by the incorporation of hydrogen atoms in the carbon network during the growth of the film what is usually taken as an indication 87
for softening of the film. This work is additionally extended to investigations of the growth process of amorphous hydrogenated film in the presence of particles. During the deposition process in the mixture of acetylene and molecular hydrogen polymerization occurs in the plasma volume (formation of particles) and on the surfaces (growth of the film). From the comparison of the temporal evolution of these two processes it can be observed that the growth of the deposited film is out-of-phase with the periodicity of the particle formation. This is due to the permanent competition between the particles and the surface of the growing film for the growth precursors. This work contains the results of the fist time done investigations of the role of hydrogen atoms in the very early stage of the volume polymerization process of hydrocarbon nanoparticle formation. More precisely, the attention is payed to chemistry of the polymerization process and to studding of the suppression of particle formation after the injection of additional flux of hydrogen atoms by reconverting the precursor radicals C 2 H into acetylene molecules. Not only the influence of hydrogen atoms on the volume polymerization process but also the influence of hydrogen atoms on the surface polymerization, i.e. the film growth under the plasma conditions is studied. 88